WO2015181698A2 - A trickle-bed reactor for purifying gas and a method of purifying gas - Google Patents

A trickle-bed reactor for purifying gas and a method of purifying gas Download PDF

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Publication number
WO2015181698A2
WO2015181698A2 PCT/IB2015/053798 IB2015053798W WO2015181698A2 WO 2015181698 A2 WO2015181698 A2 WO 2015181698A2 IB 2015053798 W IB2015053798 W IB 2015053798W WO 2015181698 A2 WO2015181698 A2 WO 2015181698A2
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Prior art keywords
gas
characteristic
packing
bed
tank
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PCT/IB2015/053798
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French (fr)
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WO2015181698A3 (en
Inventor
Grażyna BARTELMUS
Rafal SARZYNSKI
Agnieszka GĄSZCZAK
Mieczysław JAROSZYNSKI
Manfred JASCHIK
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Instytut Inzynierii Chemicznej Polskiej Akademii Nauk
Ichemad-Profarb Sp. Z O.O.
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Publication of WO2015181698A2 publication Critical patent/WO2015181698A2/en
Publication of WO2015181698A3 publication Critical patent/WO2015181698A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the subject of the invention is a trickle-bed reactor and a method of purifying gas particularly the air from volatile organic compounds and their sparingly water soluble mixtures.
  • US 5656494 patent description discloses a biofilter for the removal of contaminants from emitted gas streams.
  • the biofilter makes use of a series of trays, each containing a gas-contacting medium for removing at least one contaminant from the process stream.
  • the trays have a modular design that allows them to be sealingly stacked and to be configured to allow series, parallel or series-parallel flow through the biofilter.
  • EP 1234609 A1 patent description discloses a biological deodorizing apparatus that has an inlet portion, a treating portion and an outlet portion in series, and biologically deodorizes gas in the said treating portion.
  • Each of the portions of the apparatus is composed of one or more rectangular frames forming a cuboid, the said frames being constructed by connecting frame members and joints.
  • the treating portion is constructed containing cartridges being set by porous plastic sheets in parallel with each other at a distance which allows them to be pulled out free in horizontal direction.
  • the treating portion's blow-off surfaces are connected to the lower located blow-in surfaces of the outlet portion in an airtight way, and the open surfaces are sealed with seal panels. Water is supplied to the upper portion of the treating portion, and drained off through the bottom portion.
  • VOCs volatile organic compounds
  • sludge treatment works for treating the sludges that result from the purification, and/or industrial waste treatment works, according to which: two immiscible washing liquids (one of which is aqueous and the other an oil) are used simultaneously and are contained in a single tank; the two liquids are transferred to the head of a spraying reactor that may or may not contain packing; the two liquids are sprayed as small-diameter droplets; the air charged with volatile compounds to be absorbed is flowed counter-currently to the sprayed fluids; the absorbing fluid is recirculated, and the two washing liquids are renewed.
  • two immiscible washing liquids one of which is aqueous and the other an oil
  • the description in patent application of the WO20014023877 invention discloses a method of purifying a gas stream derived from a process wherein a glyceride containing raw-material is converted to hydrocarbon paraffins.
  • the gas stream contains hydrogen or carbon dioxide as a major component and at least one sulphurous component selected from sulphide compounds as an impurity.
  • the gas is contacted with an acidic aqueous wash solution containing transition metal ions capable of binding to sulphide ions; a significant portion of the sulphide compounds contained in the gas are bound into insoluble metal sulphide thus purifying the gas, which is recovered.
  • the method will efficiently lower sulphide concentrations to ppm or sub-ppm or even lower level and it can be implemented on an industrial scale with low investment costs.
  • the metal can be recovered.
  • the description in patent application of the EP1012253 (A1 ) invention relates to the use of microorganisms for biodegrading contaminants and discloses examples of its application.
  • the invention relates to selected microorganisms capable of biodegrading organic or inorganic contaminants present in soils (solids), liquids or gases.
  • the contaminants include priority pollutants including highly volatile organic compounds (VOCs), recalcitrant organic contaminants or inorganic contaminants such as ammonia or sulfides.
  • the invention particularly relates to biodegradation of organic contaminants by microorganisms from the groups fungus, Nocardioforms/Actinomycetes and Pseudomonadacae, either alone or in combination, which biodegrade the contamination in either the solid/soil, gas/vapor or liquid/water phases; and the transformation of inorganic contaminants, such as ammonia by Nitrosomonas spp. and Nitrobacter spp. to nitrate with optional denitrification, and hydrogen sulfide to elemental sulfur by Beggiatoa spp. and/or Thiosphera pantotropha. Porous media and cord media are used to construct the reaction sites.
  • the subject of the invention is the construction of a reactor and a method of eliminating volatile organic compounds from post reaction gases after chemical or physical processes.
  • a trickle-bed reactor for purifying gas according to the invention is characteristic in that in the tank there is at least one layer of inert packing covered with an active biofilm of microorganisms and a sprinkler placed in the top part of the tank between the gas inlet and the packing, wherein the outlet of the purified gas is located in the bottom part of the side surface of the tank, and in the cone- shaped bottom there are valves for the system controlling the level of the circulating liquid.
  • the free volume of the packing is greater than 0,8 and its specific surface area is greater than 100 m 2 /m 3 .
  • the free volume of the packing is 0,9-0,95 and its specific surface area is greater than 1 10 m 2 /m 3 .
  • the inert packing bed is placed in baskets.
  • the sprinkler has a minimum of 150 sprinkling points per m 2 of the column section and the gas is distributed evenly around each sprinkling point.
  • the method of purifying gas from volatile organic compounds in ambient temperature according to the invention is characteristic in that the gas is transported cocurrently with the liquid through the inert packing bed covered with an active biofilm of microorganisms, wherein the packing bed is being continuously sprinkled with mineral salts solution in the amount ranging between 5 and 20 m 3 /m 2 h, and the gas to be purified is distributed evenly around each sprinkling point.
  • the packing bed is being sprinkled with mineral salts solution used in the amount of 8- 9 m 3 /m 2 h.
  • the mineral salts solution contains 5-15 mass% of silicon oil with a viscosity of 100 cSt.
  • the main advantage of the invention is the construction of the trickle-bed reactor, which allows purifying large streams of gas using cocurrent downward flow of gas and liquid without the danger of flooding the column. Moreover by adjusting the number of layers of the packing it is possible to ensure that the residence time of the reaction mixture in the packing bed is appropriate for the contamination which is being eliminated. It is also important that in the presented solution the liquid sprinkling the packing bed provides the microorganisms with nutrients as well as removes from the packing bed the products of decomposition of the contaminants which are harmful to the microorganisms. The said products of decomposition may be removed or neutralized in the circulating liquid tank.
  • the trickle-bed reactor according to the invention is easy to control and regulate the operating parameters. It is also easy to control the surplus of the biomass in the packing. In order to remove it, it is enough to flush the packing bed with a stream of liquid 50% greater than that used in the process.
  • Fig.1 presents a section of the reactor
  • Fig. 2 presents a bottom view of the sprinkler
  • Fig. 3 presents a side view to a section of the sprinkler
  • Fig. 4 presents the construction of a sprinkling point with the gas flowing around it;
  • Fig. 5 presents a graph showing the conversion rate of styrene during the process of gas purification (embodiment 1 of the invention);
  • Fig. 6 presents a graph showing the conversion rate of contaminants during the process of gas purification (embodiment 2 and 3 of the invention).
  • a trickle-bed reactor with air flow capacity of 200 m 3 /h operating with cocurrent flow of gas and liquid comprises a tank 1 in which are placed three layers of inert packing 3 in the form of polypropylene ralu rings of free volume of 0,95 and specific surface area of 1 10 m 2 /m 3 . Each of the 0,6 m high layers of inert packing 3 was placed on a grid. Such an amount of packing ensured that the gas mixture remained in the reactor for 40 - 62s, which is necessary to mineralize the contaminants. The surface of the packing was inoculated with Pseudomonas sp. bacteria.
  • the sprinkler 2 which is located in the top part of the tank 1 between the gas inlet 4 and the packing 3 comprises 200 sprinkling points per m 2 of column section. Contaminated air is distributed evenly around each sprinkling point.
  • the outlet of purified air 5 is located in the bottom part of the side surface of the tank 1, whereas in the cone-shaped bottom 6 there are valves 7 for the system controlling the level of the circulating liquid.
  • the bottom 6 is filled with a solution to such a level that all of the purified air is directed to the outlet 5.
  • the trickle-bed reactor was operating continuously for approximately 150 days, removing styrene from the air, where the concentration of styrene in the inlet stream varied within the 0,5 - 1 g/m 3 range.
  • the parameters were being continually controlled and adjusted electronically using the controlling system 8.
  • a trickle-bed reactor with air flow capacity of 200 m 3 /h operating with cocurrent flow of gas and liquid comprises a tank 1 in which are placed three layers of inert packing 3 in the form of polypropylene ralu rings of free volume of 0,95 and specific surface area of 1 10 m 2 /m 3 .
  • Each of the 0,6 m high layers of inert packing 3 was placed in a basket.
  • On the packing 3 a mixed population of microorganisms was inoculated, adapted to utilizing the styrene/xylene mixture. Such an amount of packing ensured that the gas mixture remained in the reactor for 62s.

Abstract

The subject of the invention is a trickle-bed reactor and a method of purifying gas particularly the air from volatile organic compounds and their sparingly water soluble mixtures.A trickle-bed reactor for purifying gas according to the invention is characteristic in that in the tank (1) there is at least one layer of inert packing (3) covered with an active biofilm of microorganisms and a sprinkler (2) placed in the top part of the tank (1) between the gas inlet (4) and the packing (3), wherein the outlet of the purified gas (5) is located in the bottom part of the side surface of the tank (1), and in the cone-shaped bottom (6) there are valves (7) for the system controlling the level of the circulating liquid. The method of purifying gas is characteristic in that the gas is transported cocurrently with the liquid through aninert packing bedcovered with an active biofilter of microorganisms, wherein the packing bed is being continuously sprinkled with mineral salts solution in the amount ranging between 5 and 20 m3/m2 h, and the gas to be purified is distributed evenly around each sprinkling point.

Description

A trickle-bed reactor for purifying gas
and a method of purifying gas
The subject of the invention is a trickle-bed reactor and a method of purifying gas particularly the air from volatile organic compounds and their sparingly water soluble mixtures.
US 5656494 patent description discloses a biofilter for the removal of contaminants from emitted gas streams. The biofilter makes use of a series of trays, each containing a gas-contacting medium for removing at least one contaminant from the process stream. The trays have a modular design that allows them to be sealingly stacked and to be configured to allow series, parallel or series-parallel flow through the biofilter.
EP 1234609 A1 patent description discloses a biological deodorizing apparatus that has an inlet portion, a treating portion and an outlet portion in series, and biologically deodorizes gas in the said treating portion. Each of the portions of the apparatus is composed of one or more rectangular frames forming a cuboid, the said frames being constructed by connecting frame members and joints. The treating portion is constructed containing cartridges being set by porous plastic sheets in parallel with each other at a distance which allows them to be pulled out free in horizontal direction. The treating portion's blow-off surfaces are connected to the lower located blow-in surfaces of the outlet portion in an airtight way, and the open surfaces are sealed with seal panels. Water is supplied to the upper portion of the treating portion, and drained off through the bottom portion.
The description in patent application of the WO2008/152222 invention discloses a process for eliminating volatile compounds, in particular volatile organic compounds (VOCs), from the air emitted by effluent or wastewater purification plants, and/or sludge treatment works for treating the sludges that result from the purification, and/or industrial waste treatment works, according to which: two immiscible washing liquids (one of which is aqueous and the other an oil) are used simultaneously and are contained in a single tank; the two liquids are transferred to the head of a spraying reactor that may or may not contain packing; the two liquids are sprayed as small-diameter droplets; the air charged with volatile compounds to be absorbed is flowed counter-currently to the sprayed fluids; the absorbing fluid is recirculated, and the two washing liquids are renewed.
The description in patent application of the WO20014023877 invention discloses a method of purifying a gas stream derived from a process wherein a glyceride containing raw-material is converted to hydrocarbon paraffins. The gas stream contains hydrogen or carbon dioxide as a major component and at least one sulphurous component selected from sulphide compounds as an impurity. According to the invention, the gas is contacted with an acidic aqueous wash solution containing transition metal ions capable of binding to sulphide ions; a significant portion of the sulphide compounds contained in the gas are bound into insoluble metal sulphide thus purifying the gas, which is recovered. The method will efficiently lower sulphide concentrations to ppm or sub-ppm or even lower level and it can be implemented on an industrial scale with low investment costs. The metal can be recovered.
The description in patent application of the EP1012253 (A1 ) invention relates to the use of microorganisms for biodegrading contaminants and discloses examples of its application. The invention relates to selected microorganisms capable of biodegrading organic or inorganic contaminants present in soils (solids), liquids or gases. The contaminants include priority pollutants including highly volatile organic compounds (VOCs), recalcitrant organic contaminants or inorganic contaminants such as ammonia or sulfides. The invention particularly relates to biodegradation of organic contaminants by microorganisms from the groups fungus, Nocardioforms/Actinomycetes and Pseudomonadacae, either alone or in combination, which biodegrade the contamination in either the solid/soil, gas/vapor or liquid/water phases; and the transformation of inorganic contaminants, such as ammonia by Nitrosomonas spp. and Nitrobacter spp. to nitrate with optional denitrification, and hydrogen sulfide to elemental sulfur by Beggiatoa spp. and/or Thiosphera pantotropha. Porous media and cord media are used to construct the reaction sites.
The subject of the invention is the construction of a reactor and a method of eliminating volatile organic compounds from post reaction gases after chemical or physical processes.
A trickle-bed reactor for purifying gas according to the invention is characteristic in that in the tank there is at least one layer of inert packing covered with an active biofilm of microorganisms and a sprinkler placed in the top part of the tank between the gas inlet and the packing, wherein the outlet of the purified gas is located in the bottom part of the side surface of the tank, and in the cone- shaped bottom there are valves for the system controlling the level of the circulating liquid.
Favourably, the free volume of the packing is greater than 0,8 and its specific surface area is greater than 100 m2/m3.
Also favourably, the free volume of the packing is 0,9-0,95 and its specific surface area is greater than 1 10 m2/m3.
It is recommended to place the inert packing bed on grids.
Favourably, the inert packing bed is placed in baskets.
Favourably, the sprinkler has a minimum of 150 sprinkling points per m2 of the column section and the gas is distributed evenly around each sprinkling point. The method of purifying gas from volatile organic compounds in ambient temperature according to the invention is characteristic in that the gas is transported cocurrently with the liquid through the inert packing bed covered with an active biofilm of microorganisms, wherein the packing bed is being continuously sprinkled with mineral salts solution in the amount ranging between 5 and 20 m3/m2 h, and the gas to be purified is distributed evenly around each sprinkling point.
Favourably, the packing bed is being sprinkled with mineral salts solution used in the amount of 8- 9 m3/m2h.
Also favourably, the mineral salts solution contains 5-15 mass% of silicon oil with a viscosity of 100 cSt.
The main advantage of the invention is the construction of the trickle-bed reactor, which allows purifying large streams of gas using cocurrent downward flow of gas and liquid without the danger of flooding the column. Moreover by adjusting the number of layers of the packing it is possible to ensure that the residence time of the reaction mixture in the packing bed is appropriate for the contamination which is being eliminated. It is also important that in the presented solution the liquid sprinkling the packing bed provides the microorganisms with nutrients as well as removes from the packing bed the products of decomposition of the contaminants which are harmful to the microorganisms. The said products of decomposition may be removed or neutralized in the circulating liquid tank.
The trickle-bed reactor according to the invention is easy to control and regulate the operating parameters. It is also easy to control the surplus of the biomass in the packing. In order to remove it, it is enough to flush the packing bed with a stream of liquid 50% greater than that used in the process.
The subject of the invention in non-restrictive embodiments is presented in the drawing, where:
Fig.1 presents a section of the reactor;
Fig. 2 presents a bottom view of the sprinkler;
Fig. 3 presents a side view to a section of the sprinkler;
Fig. 4 presents the construction of a sprinkling point with the gas flowing around it; Fig. 5 presents a graph showing the conversion rate of styrene during the process of gas purification (embodiment 1 of the invention);
Fig. 6 presents a graph showing the conversion rate of contaminants during the process of gas purification (embodiment 2 and 3 of the invention).
Embodiment 1.
A trickle-bed reactor with air flow capacity of 200 m3/h operating with cocurrent flow of gas and liquid comprises a tank 1 in which are placed three layers of inert packing 3 in the form of polypropylene ralu rings of free volume of 0,95 and specific surface area of 1 10 m2/m3. Each of the 0,6 m high layers of inert packing 3 was placed on a grid. Such an amount of packing ensured that the gas mixture remained in the reactor for 40 - 62s, which is necessary to mineralize the contaminants. The surface of the packing was inoculated with Pseudomonas sp. bacteria. The sprinkler 2, which is located in the top part of the tank 1 between the gas inlet 4 and the packing 3 comprises 200 sprinkling points per m2 of column section. Contaminated air is distributed evenly around each sprinkling point. The outlet of purified air 5 is located in the bottom part of the side surface of the tank 1, whereas in the cone-shaped bottom 6 there are valves 7 for the system controlling the level of the circulating liquid. The bottom 6 is filled with a solution to such a level that all of the purified air is directed to the outlet 5. The trickle-bed reactor was operating continuously for approximately 150 days, removing styrene from the air, where the concentration of styrene in the inlet stream varied within the 0,5 - 1 g/m3 range. The reactor was being sprinkled with a mineral salts solution in the amount of 8,4 m3/m2h, with pH =7, temperature (t= 30°C) and ammonia nitrogen content (~0,04 g/l). The parameters were being continually controlled and adjusted electronically using the controlling system 8.
At 24h intervals 10-15% of the volume of the mineral salts solution circulating in the installation was replaced with a fresh mineral salts solution containing ammonium salts, phosphates and microelements, which provided the microorganisms with nutrients necessary for proper functioning.
During the testing the styrene conversion rate remained constant at the level of approx. 0,8 at empty bed residence time (EBRT) of τ = 41 s and at the level of 0,9 - 0,95 at EBRT of τ = 62s. Measurement results are presented in Fig. 5. There was no styrene or any intermediate products of its mineralization found in the circulating liquid. There were also no drastic changes in pressure drop of the gas in the packing bed, which would signify that the bed is being blocked by a surplus of biomass. This means that the shear stress of the cocurrently flowing liquids is removing the surplus of the biomass from the packing on an ongoing basis.
Embodiment 2
A trickle-bed reactor with air flow capacity of 200 m3/h operating with cocurrent flow of gas and liquid comprises a tank 1 in which are placed three layers of inert packing 3 in the form of polypropylene ralu rings of free volume of 0,95 and specific surface area of 1 10 m2/m3. Each of the 0,6 m high layers of inert packing 3 was placed in a basket. On the packing 3 a mixed population of microorganisms was inoculated, adapted to utilizing the styrene/xylene mixture. Such an amount of packing ensured that the gas mixture remained in the reactor for 62s. The efficiency of the reactor was tested for 200 days with the gas mixture remaining in the reactor for the duration of τ= 62s and the packing bed being sprinkled with mineral salts solution in the amount of 8,4 m3/m2h, whose parameters were being closely monitored. Process efficiency ranged between 43-47% in the case of xylene and between 83-88 % in the case of styrene. Measurement results are presented in Fig. 5. Embodiment 3
The tests were carried out in a trickle-bed reactor in conditions described in embodiment 2. 7,5 wt% of silicon oil with a viscosity of 100 cSt was added to the circulating mineral salts solution. The conversion rate of both contaminants increased and after about 10 days stabilized at the level of 0,78 in the case of xylene and of 0,985 in the case of styrene. Measurement results are presented in Fig.6.

Claims

Claims
1 . A trickle-bed reactor for purifying gas, characteristic in that in the tank (1_) there is at least one layer of inert packing (3) covered with an active biofilm of microorganisms and a sprinkler (2) placed in the top part of the tank (1 ) between the gas inlet (4) and the packing (3), wherein the outlet of the purified gas (5) is located in the bottom part of the side surface of the tank (V), and in the cone-shaped bottom (6) there are valves (7) for the system controlling the level of the circulating liquid.
2. A reactor according to claim 1 , characteristic in that the free volume of the inert packing (3) is greater than 0,8 and its specific surface area is greater than 100 m2/m3.
3. A reactor according to claim 2, characteristic in that the free volume of the inert packing (3) is 0,9-0,95 and its specific surface area is greater than 1 10 m2/m3.
4. A reactor according to claims 1 and 2, characteristic in that the inert packing bed (3) is placed on grids.
5. A reactor according to claims 1 and 2, characteristic in that the inert packing bed (3) is placed in baskets.
6. A reactor according to claim 1 , 2 or 3, characteristic in that the sprinkler (2) has a minimum of 150 sprinkling points per m2 of the column section and the gas is distributed evenly around each sprinkling point.
7. A method of purifying gas from volatile organic compounds in ambient temperature, characteristic in that the gas is transported cocurrently with the liquid through the inert packing bed covered with an active biofilm of microorganisms, wherein the packing bed is being continuously sprinkled with mineral salts solution in the amount ranging between 5 and 20 m3/m2 h, and the gas to be purified is distributed evenly around each sprinkling point.
8. A method of purifying gas according to claim 7, characteristic in that the packing bed is being sprinkled with mineral salts solution used in the amount of 8- 9 m3/m2h.
9. A method according to claims 7 and 8, characteristic in that the mineral salts solution contains 5 - 15 mass% of silicone oil with a viscosity of 100 cSt.
PCT/IB2015/053798 2014-05-26 2015-05-22 A trickle-bed reactor for purifying gas and a method of purifying gas WO2015181698A2 (en)

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PL408337A PL231112B1 (en) 2014-05-26 2014-05-26 Biological trickle-bed reactor for purification of gas method for purification of gas
PLP.408337 2014-05-26

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CN106039983A (en) * 2016-07-13 2016-10-26 盐城工学院 Biofilm formation starting method of biotrickling system for degrading hydrophobic and volatile organic compounds
WO2019046188A1 (en) * 2017-08-28 2019-03-07 Icm, Inc. Gas fermentation using multiple-pass trickle bed reactors
CN113181761A (en) * 2021-06-01 2021-07-30 国投信开水环境投资有限公司 Charcoal filler biological deodorization device

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